Hui-Ming Hung

The size effect of hematite and corundum inclusions on the efflorescence relative humidities of aqueous ammonium sulfate particles

Mineral dusts inside aqueous atmospheric particles provide surfaces that induce crystallization during episodes of decreasing relative humidity (RH). Submicron aqueous ammonium sulfate particles containing hematite (α-Fe 2 O 3 ) and corundum (α-Al 2 O 3 ) inclusions are investigated in an aerosol flow tube at 298 K. As compared to 35% RH where homogeneous nucleation is rapid, the heterogeneous nuclei regulate the RH from 35% up to 60% RH as the inclusion size varies from 50 to 450 nm. The strong size dependence can be rationalized by an active site model. Model optimization yields 10 10.4 sites cm -2 and m < 0 for α-Al 2 O 3 and 10 9 sites cm -2 and m = 0.04 for α-Fe 2 O 3 particles.

Effects of temperature and physical state on heterogeneous oxidation of oleic acid droplets with ozone.

The heterogeneous reactions of pure micrometer-sized oleic acid droplets with ozone were studied as a function of temperature and physical state. Oxidation reactions were monitored using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT-IR) and UV-vis spectrometry. Variations in droplet morphology due to the extent of oxidation were monitored using an optical microscope. Oleic acid droplets were maintained in either solid or liquid state at 9.0 °C. The physical state of the aerosol was determined from the IR absorbance spectra. Oxidation of solid state oleic acid with ozone at 9.0 °C was rapidly converted to the liquid state, which was most likely due to the presence of oxidation products on the surface of the droplets. The fast melting process that resulted from exposure of solid-phase droplets to ozone produced an oxidation rate similar to that for liquid-phase droplets exposed to ozone at the same temperature. Analysis of the carboxylic IR absorbance ratio for esters vs carboxylic acids indicates that the larger ester C═O-to-carboxylic acid C═O ratios at higher temperature appeared to correspond to the production of α-acyloxyalkyl hydroperoxide oligomers and polymers. The wide variation in product yields will result in vastly different physical properties of aerosol particles under different ambient environmental conditions.

Infrared Spectroscopic Evidence for the Ice Formation Mechanisms Active in Aerosol Flow Tubes

Interest in quantifying processes of ice formation in the atmosphere has led to the recent development of new laboratory techniques, including an aerosol flow tube (AFT) reactor employed for the study of the ice nucleation kinetics of suspended submicrometer aqueous particles. The AFT technique employs an infrared (IR) beam along the flow tube axis. Spectral changes between 700 and 6000 cm−1 indicate the formation of ice at sufficiently cool temperatures. Apparent freezing temperatures are determined as a function of condensed-phase mole fraction composition. A typical aqueous chemical system is (NH4)2SO4/H2O. The mole fraction composition of the condensed-phase of this aerosol is determined by the ratio of the integrated spectroscopic bands for H2O and SO42–. A key uncertainty in the AFT-IR technique is the freezing mechanism, and knowledge of the mechanism is essential to estimate homogeneous nucleation rates (J, cm−3 s−1) from observed apparent freezing temperatures. The current work provides observational and modeling spectral evidence, based upon changes in the scattering component of the recorded IR extinction spectra with temperature, that observed ice freezing events at warmer temperatures arise from the following mechanism: relatively few particles in the aerosol freeze (e.g., 1 in 106) and this primary event is followed by rapid scavenging of water vapor to grow the few ice particles into large ice particles observed in the IR spectra. Correspondingly, the remaining aqueous particles partially evaporate. In contrast, the spectral evidence provides support that a modified mechanism is operative at cooler temperatures: the ice freezing event consists of the freezing of a much larger fraction of the particles (e.g., 1 in 10) accompanied by a much less important vapor-phase mass transfer event.

Oxidation of Gas-Phase SO2 on the Surfaces of Acidic Microdroplets: Implications for Sulfate and Sulfate Radical Anion Formation in the Atmospheric Liquid Phase

The oxidation of SO2(g) on the interfacial layers of microdroplet surfaces was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer. Four major ions, HSO3(-), SO3(•-), SO4(•-) and HSO4(-), were observed as the SO2(g)/N2(g) gas-mixture was passed through a suspended microdroplet flow, where the residence time in the dynamic reaction zone was limited to a few hundred microseconds. The relatively high signal intensities of SO3(•-), SO4(•-), and HSO4(-) compared to those of HSO3(-) as observed at pH < 3 without addition of oxidants other than oxygen suggests an efficient oxidation pathway via sulfite and sulfate radical anions on droplets possibly via the direct interfacial electron transfer from HSO3(-) to O2. The concentrations of HSO3(-) in the aqueous aerosol as a function of pH were controlled by the deprotonation of hydrated sulfur dioxide, SO2·H2O, which is also affected by the pH dependent uptake coefficient. When H2O2(g) was introduced into the spray chamber simultaneously with SO2(g), HSO3(-) is rapidly oxidized to form bisulfate in the pH range of 3 to 5. Conversion to sulfate was less at pH < 3 due to relatively low HSO3(-) concentration caused by the fast interfacial reactions. The rapid oxidation of SO2(g) on the acidic microdroplets was estimated as 1.5 × 10(6) [S(IV)] (M s(-1)) at pH ≤ 3. In the presence of acidic aerosols, this oxidation rate is approximately 2 orders of magnitude higher than the rate of oxidation with H2O2(g) at a typical atmospheric H2O2(g) concentration of 1 ppb. This finding highlights the relative importance of the acidic surfaces for SO2 oxidation in the atmosphere. Surface chemical reactions on aquated aerosol surfaces, as observed in this study, are overlooked in most atmospheric chemistry models. These reaction pathways may contribute to the rapid production of sulfate aerosols that is often observed in regions impacted by acidic haze aerosol such as Beijing and other megacities around the world.

Apparent freezing temperatures modeled for several experimental apparatus

Ice formation by homogeneous nucleation in aqueous atmospheric particles composed of high ionic strength electrolytes is at times believed to be the dominant initiation step in cirrus and polar stratospheric cloud formation. Microphysical models of ice nucleation occurring during atmospheric processes are based upon volume nucleation rates, J(T, x), measured in laboratory experiments where T is temperature and x is mole fraction salt composition. At the present time, there are large discrepancies among apparent freezing temperatures reported by several investigators employing different experimental apparatus. One current hypothesis is that a common J function is expressed differently in these several techniques, which have variations in observation times, system volumes, vapor mass transfer, and so on. In the current paper, we model the several experiments based on a common J function and simulate apparent freezing temperatures of H 2 SO 4 /H 2 O and (NH 4 ) 2 SO 4 /H 2 O particles. We find that the experimental results can be categorized into two groups, one of which is consistent with a function J, and the other with J 2 , while J 1 and J 2 are mutually exclusive. We thus conclude no single J function exists that can simultaneously simulate all reported experimental results, thus refuting the previously proposed common J hypothesis for the reconciliation of experimental results.

Reactive aging of films of secondary organic material studied by infrared spectroscopy.

The reactive aging of films of secondary organic material (SOM) to ozone, irradiation, and water was studied by attenuated total reflectance infrared spectroscopy (ATR-IR). The films were prepared by deposition onto the ATR elements of particles produced by reaction of isoprene with hydroxyl radicals and of α-pinene with ozone in the Harvard Environmental Chamber (HEC). The infrared spectra showed that the isoprene-derived film had strong hydroxyl absorptions whereas the α-pinene-derived film had strong carbonyl absorptions. The organic films were exposed to dry and humid flows of ozone, as well as to ultraviolet irradiation, to mimic reactive aging processes that can occur in the troposphere. Both the isoprene- and α-pinene-derived films were nonreactive with respect to ozone exposure, for both dry and humid conditions, indicating that the secondary organic material consisted mostly of saturated organic species. Both films, however, were susceptible to aging by ultraviolet radiation possibly due to the presence of organic hydroperoxides, and all functional groups other than carbonyls decreased upon irradiation. In regard to hygroscopicity, as a benchmark the ratio x(W_CO) for oxalic acid of the intensity of the water-bending peak to that of carbonyl absorption (arising from carboxylic acids) was recorded from 20% to 80% relative humidity (RH). This quantity was then also measured for the isoprene- and α-pinene-derived organic films. The result of (x(W_CO))(isoprene) > (x(W_CO))(benchmark) across the range of studied RH values shows that species other than carboxylic acids contributed significantly to the hygroscopicity of the isoprene-derived film. The spectra were consistent with alcohols and hydroperoxides as the hygroscopic components. By comparison, the result of (x(W_CO))(pinene) ≈ (x(W_CO))(benchmark) indicates a dominance of carboxylic acids with respect to the hygroscopicity of this film.

Surface fractal dimension, water adsorption efficiency, and cloud nucleation activity of insoluble aerosol

Surface porosity affects the ability of a substance to adsorb gases. The surface fractal dimension D is a measure that indicates the amount that a surface fills a space, and can thereby be used to characterize the surface porosity. Here we propose a new method for determining D, based on measuring both the water vapour adsorption isotherm of a given substance, and its ability to act as a cloud condensation nucleus when introduced to humidified air in aerosol form. We show that our method agrees well with previous methods based on measurement of nitrogen adsorption. Besides proving the usefulness of the new method for general surface characterization of materials, our results show that the surface fractal dimension is an important determinant in cloud drop formation on water insoluble particles. We suggest that a closure can be obtained between experimental critical supersaturation for cloud drop activation and that calculated based on water adsorption data, if the latter is corrected using the surface fractal dimension of the insoluble cloud nucleus.

DESIGN PARAMETERS OF DUAL-STAGE ION REFLECTRONS

Exact solutions of the second‐order differential equation describing the energy dependence of ion flight time in a reflectron time‐of‐flight mass spectrometer are derived, from which numerical evaluation of the construction and operation parameters of a dual‐stage reflectron can easily be performed. Considerations in choosing the design parameters are discussed.

The Reactivity of Toluene-Derived Secondary Organic Material with Ammonia and the Influence of Water Vapor

The atmospheric reactions of secondary organic material (SOM) with gaseous reactants alter its composition and properties, which can further impact the Earth system. To investigate how water content and precursor affect the reactivity of SOM, the reaction between toluene-derived SOM and ammonia for variable relative humidity (RH) was investigated. A Fourier transform infrared spectrometer was used to monitor the absorbance change of the functional groups as a function of exposure time. There was a fast response to water vapor compared with a gradual spectral variation associated with ammonia uptake. When RH is higher than 25 ± 5%, the spectral changes across 1500-1900 cm-1 showed a decreasing trend for carboxylic acids and an increasing trend for carboxylates, suggesting a neutralization reaction by ammonia uptake. The observed increasing trend for the region of 1270-1360 cm-1 might be associated with amines and suggests the formation of organonitrogen compounds for the toluene-derived SOM aging by ammonia at high RH. The corresponding intensity change of C-O groups (1000-1260 cm-1) with the increased liquid water content as RH increases at the first 6 min suggested that the possible chemical reactions, such as hydrolysis of acetals and hemiacetals to aldehydes and alcohols or esters to carboxylic acids and alcohols, might change the diffusivity of particles and affect the ammonia uptake. The threshold point of ammonia uptake at 30% RH was consistent with a more significant absorbance change of liquid water content and C-O groups at RH ≥ 35 ± 5%. For comparison between anthropogenic and biogenic precursor gases, an isoprene-derived SOM film was also studied. It was more volatile and reactive to ammonia than the toluene-derived SOM. This result implies that the diffusion of ammonia was faster inside isoprene-derived SOM. Overall, the chemical reactions of SOM particles during their atmospheric residence time are precursor- and RH-dependent, which may alter the current understanding of their impact on the Earth system.

Quantification of SO2 Oxidation on Interfacial Surfaces of Acidic Micro-Droplets: Implication for Ambient Sulfate Formation

Sulfate formation on the surface of aqueous microdroplets was investigated using a spray-chamber reactor coupled to an electrospray ionization mass spectrometer that was calibrated using Na2SO4(aq) as a function of pH. The observed formation of SO3-•, SO4-•, and HSO4- at pH < 3.5 without the addition of other oxidants indicates that an efficient oxidation pathway takes place involving direct interfacial electron transfer from SO2 to O2 on the surface of aqueous microdroplets. Compared to the well-studied sulfate formation kinetics via oxidation by H2O2(aq), the interfacial SO42- formation rate on the surface of microdroplets was estimated to be proportional to the collision frequency of SO2 with a pH-dependent efficiency factor of 5.6 × 10-5[H+]3.7/([H+]3.7+10-13.5). The rate via the acidic surface reactions is approximately 1-2 orders of magnitude higher than that by H2O2(aq) for a 1.0 ppbv concentration of H2O2( g) interacting with 50 μg/m3 of aerosols. This finding highlights the relative importance of the interfacial SO2 oxidation in the atmosphere. Chemical reactions on the aquated aerosol surfaces are overlooked in most atmospheric chemistry models. This interfacial reaction pathway may help to explain the observed rapid conversion of SO2 to sulfate in mega-cities and nearby regions with high PM2.5 haze aerosol loadings.